Polymerization of olefins



2 sheets-sheet 1 C.:.G.GF.RHO1 Dl Filed' Deo. 12, 1938 POLYMERIZATION 0F OLEFINS w V fw fw w.

July 28, 1942.

July 28, 1942 c.' G. GERHOLD POLYMERIZATION OF OLEFINS `Filed Dec. 12, 1958 2 Sheets-Sheet 2 Patented July 28, 1942 UNITED STATES PATENT OFFICE 2,291,216 POLYMERZATION 0F OLEFINS clarence G. Gel-hola, chicago, 1u., assigner to Universal OilProducts Company, Chicago, Ill., a corporation of Delaware f Application December 12, 1938, Serial No.I 245,196

3 Claims.

This invention relates particularly to the manufacture of iso-octanes or hydrocarbon mixtures containing relatively high percentages of isooctanes from normally gaseous olefin hydrocarbons.

Primarily, it is concerned witha process involving a succession of closely co-operating steps whereby maximum yields of iso-octanes having a relatively high octane value are produced from relatively close cut hydrocarbon fractions com- `prising butanes and butenes commonly known to the oil industry as B-B fractions. These fractions are producible from 'the hydrocarbon mixtures evolved as overhead vapors in the stabilization of primary cracked distillates. The process is also applicable to mixtures of 4-carbon atom hydrocarbons containing varying percentages of olens'produced in yany other manner such as, for example, the dehydration of butyl lalcohols or the partial or complete dehydrogenation or cracking of butanes. More specifically it is concerned with a process for regulating and controlling the extent of the reaction during the polymerization step` of ythe process for the production of iso-octane in order to produce a maximum yield of iso-octane having high octane value.

The iso-parains and particularly the isooctanes are at prsent a very desirable fuel for aviation engines on account of their high antiknock value, medium boiling range, and stability in respect to gummy and resinous deposits which may cause trouble in fuel feed systems. They are also sought after as blending fluids for increasing the antiknock value of 'motor fufls which are below grade in this respect. The present process permits the maximum utilization of the Ll-carbon atoms in the aforesaid B-B fractions for the production of iso-octane mixtures in which the major constituents seem to be 2,2,4-trimethyl pentane, and 2,2,3-trimethy1 pentane, both iso-cctanes of high antiknock value. although the exact determination of the relative proportions of the diierent isomers is difcult.

The present process for the production of isooctane involves two stages: First, a polymerization stage for the polymerization of the olens in the so-called B-Bv fraction to iso-octenes,

followed by a second stage of hydrogenation of the iso-ocenes to iso-octanes. 'I'he rst stage, which involves a large amount of mixed polymerization of nand iso-butenes, is commonly call :d selective polymerization.

In one specic embodiment the present inven- Cal tion comprises processing butene-butene mixtures for the production of iso-octane by the following series of steps: v

(l) Optional preliminary treatment to remove impurities deleterious to the catalyst employed in succeeding polymerizing and Ahydrogenating stages. This usually involves washing of the liquid fraction with basic aqueous solution or with .water or with both in a two-stage washing treatment. l

(2) subjecting the charge under controlled conditions of polymerizing temperatures and pressures to contact with catalysts of increasing activity disposed in reactors which provide for removal of reaction heat to effect a controlled degree of mixed polymerizationv of the norm-al and iso-butenes.

(3) Fractionating the eiiiux from the polymerizing step to separate the polymers from the residual butanes and unreacted butenes.

4) Returning residual butanes (including unreacted butenes) to the charge if required to reduce the butene content of the mixture passing over the catalyst.

(5) Further fractionating the debutanized polymers to produce an overhead iso-octene fraction and a bottom product of heavy polymers.

(6) Hydrogenating the mixture of iso-octenes to produce iso-octanes by subjecting the isooctenes togethar with hydrogen under vapor phase superatmcspheric temperature and pressure conditions to contact with nickel-containing catalyst disposed in reactors which provide for the removal of reaction heat.

In the operation of the so-called selective polymerization stage of the process which comprises subjecting butenes to contact with polymerizing catalyst under polymerizing conditions and temperatures and pressures for the production of a polymer product containing principally iso-octenes which are then hydrogenated to produce high octane 'number iso-octenes.' I have found f that the preferred type of operation is one in which the catalyst nrst coming in Contact with the B-B fraction is weak and in 4which the strength of the catalyst gradually increases, and is very lactive near the vend of the polymerizing reaction. The use of this method of operation results in the production of a maximum octane number of iso-octane while at the same time effecting a high degree of polymerization cf the butenes to octenes. I have found that if the polymerization rate at the inlet of the polymerizing zone is high, particularly when the concentration of the more active butylenes is high,

portion of the polymerizing zone since the high concentrationof active butylenes makes it possible to obtain rapid polymerization in spite of the low catalyst activity.

As the polymerization through the catalyst bed proceeds. the concentration of the more active butylenes decreases and it then becomes necessary to contact the olenns with a catalyst having a higher activity in order to produce the desired arising conversion of butenes to octenes. Bumm the above, it is advantageous to use a catalyst mass having a graded activity, vbeing ;very weak at the inlet end of the reactor zone and very active at the outlet end. One manner of accomplishing this result is to manufacture catalyst having varied degrees of activity and place the less activecatalyst in contact with the fresh olefins undergoing polymerization and gradually using catalyst of higher activity as the olefin concentration decreases. This gives satisfactory results although it is not practical to manufacture and 'to use catalyst of varying activity and to avoid the use of prepared catalyst of varying activity I may use a catalyst of the same activity and decreasing the activity of the initial catalyst mass by passing a poisoning agent through the initial portion of the catalyst mass. This is accomplished by pretreating the catalyst mass for a definite period of time either with ammonia. amines or other basic nitrogen compounds. The

catalyst bed is preferably poisoned to such an 40 extent that it controls the initial polymeriza-v tion of oleiins when the concentration of the active olefins is high in such a manner that the octane number of the nnal hydrogenated product is not impaired.- When this point is reached it is not only no longer necessary to further poison the catalyst. but it is also harmful because any further poisoning results in a less active catalyst which in turn results in a decrease in the conversion of the butenes to octenes.

The polymerization of the butenes to octenes usuallyfoccurs in severalf reactors in series. It has been found that after the polymerization reaction has been carried out for a -sunlcient length of time that the first reactor containing the catalyst mass is no longer sufficiently active for the polymerization 'of the olenns and it is necessary to regenerate the first catalyst bed. Therefore, in order to accomplish the obiects of my invention it is necessary to. rotate the reaco0 tors in a definite manner-in order to contact the butenes undergoing polymerization with the least active catalyst while the concentration of the butenes is high, and by reactors containing catalysts of increasing activity as the concentration of the butenes decreases. This may be illustrated as follows:

Assume that there are four catalyst' reactors:

a, b, c, and d, and that catalyst reactors a, b, and

c are being used in thepolymerization stage of the process, catalyst reactor d being a standby reactor containing either fresh catalyst or regenerated catalyst. As soon as the catalyst in reactor a becomes poisoned or the activity 4of the catalyst inreactor a decreases to such a point is cut out'of the system and the reactor d containing active catalyst placed in the system after the reactor c. Thereby. the catalyst reactor b becomes the least active and is followed by the reactors c and d containing more active catalyst masses. Catalyst in reactor a is now regenerated and as soon as catalyst in reactor bloses its activity to such a point that it is no longer useful, reactor b is removed from the system and reactor a. after either'regeneration of the .catalyst contained therein or renlling with fresh catalyst is placed in the system after reactor c. This method of rotation is maintained in such a manner tha't the spent catalyst always contacts the catalyst initially and the fresh catalyst or regenerated catalyst is always placed in the final stage of the polymerizing system.

Previously it has been found advantageous to subject the butane-butene mixture prior to polymerization to a preliminary treatment to remove impurities deleterious to the catalyst employed in the succeeding polymerizing and hydrogenating stages. This usually involves washing of the liquid fractions with basic aqueous solution and in general aqueous solutions having an alkaline reaction and controlled concentration. Although this preliminary treatment is often advantageous and at times necessary, it is frequently unnecessary and in some instances harmful. I have found that by passing the butane-butene mixture without any preliminary treatment to the cataremoved in the first portion of the catalyst mass,

which weakens the catalyst and enables the process to produce a uniformly high octane number in the final iso-octane product. As soon as the catalyst in the first reactor is sufilciently poisoned that further poisoning will no longer be beneficial for the production of high octane isooctenes at the end of the hydrogenation step, the butane-butene mixture -is then subjected to preliminary treatment for the removal of ,those substances deleterious to theA catalyst since further poisoning tends to decrease the yields obtainable from the catalytic polymerization of butenes to octenes.

The above methods illustrate several ways of carrying out the objects of my invention, but I do not wish to limit my invention to any particular method for contacting the fresh butanebutene mixture to catalytic polymerization with a catalyst of progressively increasing activity.

The foregoing brief outline of the character and steps of the process will be amplified by describing a typicaloperation in connection with the attached drawings comprising Figures 1 and a line I containing a valve l through a mixer I .of ammonia, that is, from two to three grams of which may comprise a succession of perforated plates or any other type of .internal structure which will insure turbulence. Wash liquids which usually comprise. water or moderately concentrated solutions of caustic soda of from approximately 5 to 15 B. in gravity are admitted through line I containing valve II to a pump I2 which discharges through line I3 containing valve I4 into line 4 preceding the mixer The impurities commonly encountered in butanebutene fractions from cracking processes operating upon different types of petroleum oils and their fractions are usually removed by this treatment to a sutlicient degree to adequately protect the life of the catalyst. If water washing or the use of weak acids are necessary to take the place of oi' supplement the treatment with caustic soda, these steps may be employed without departing from the scope of the invention, although only a single washing step is all that is shown on the drawings.

Prior to removing reactor 28 from the system after the catalyst in this reactor loses its activity to such a point that it is no longer effective in polymerizing olens, it is usually necessary to pretreat the reactor 36 either with ammonia or with found that basic ammonia compounds are those poisons which reduce the activity of the catalyst. If any other catalyst is used, any other suitable poison may be introduced into reactor 36 prior to the time that reactor 28 is removed from the system and reactor 36 becomes the catalyst reactor which rst contacts the B-B charge. It has been found that in charging in ordinary B-B fraction containing about .0006 percentage of basic ammonia compounds that from 24 to 48 hours pre-treatment of reactor 36 prior to the time it becomes the iirst reactor in series is required in order to maintain the octane number of the nal iso-octane recovered at a maximum level.

'Inorder to provide for the pretreatment of the catalyst in any particular reactor, line 5 containing valve 6' is provided in order that a portion or all of the B-B fraction may bypass the pre-j treating step of the system by passing the B-B fraction through line 5f containing valve 6' into line I3' containing valve I 4f If it is desired to pretreat a portion of the B-B fraction and at the same time not to treat a second portion of the B--B fraction, line I5' containing valve I6 is provided for passing the untreated B-B fraction through preheater 22' into line 23'. The untreated portion of the B-B fractionmay be introduced into any of the threereactors shown, viz., 28, 36, and 48, by means of lines 24', 25', and 26', respectively, containing valves 21.', 28', and 29', respectively. In case it is desired to pretreat or treat any of the reactors with ammonia I have provided pump 1 in line 8 containing valves 9 and I0 connected to the manifold line 23.

I have found that one to two grams of ammonia per pound of catalyst is required to sufficiently reduce the Yactivity of the catalyst in reactor 35 to such a point that it no longer has a harmful effecten the octane number of the final iso-octane product. In case only fresh catalyst is available, I-have found it necessary to pretreat the lfresh catalystgwith-slightly higher amounts ammonia per pound of catalyst in order to reduce the activity of the catalyst i'lrst contacting the fresh B--B fraction in order to reduce the activity of the catalyst to such a point that a high octane number for the nal iso-octane prod'- uct can be maintained.

The mixture lof hydrocarbons and Washing fluids pass-es through line I containing valve 8 to a settling drum 9 which has a drawoff line I5 containing a valve I6 for the removal of spent or partially spent washing uids. If found advantageous, the amount of washing fluid which is passed through the mixer in admixture with the hydrocarbons may be increased without increasing the amount of fluid used by the process by recirculating the washing fluid which settles in drum 9 to the inlet line 4 of mixer 6 through line 8a, pump IIa, and line I2a containing valv I3a.

The purified hydrocarbon charge passesl through line I'I and valve I8 to a pump I9 which y through a preheater 22 wherein the temperature v polymerization of the olefrins.

is raised to the optimum point for initiating the Steam passes to the preheater 22 and condenses in indirect contact with the charge in the preheater under a pressure corresponding to the optimum temperature of treatment. The source of the steam at this point will be described later in connection with the system of temperature control.

The preheated charge is now passed under suitable pressure vto a polymerizing treatment in reactors containing polymerizing catalyst. Among preferred catalyst are precalcined mixtures of phosphoric acids and adsorbents, the latter preferably being of a siliceous character and comprising such materials as certain clays of the Montmorillonite and bentonite type (eitherraw or acid treated), kieselguhr, precipitated silica, and other siliceous and refractory materials. Granular catalyst may be prepared by making a paste, for example, of kieselguhr, and a major proportion by weight of ortho or pyrophosphoric acid, calcining the mixture at temperatures from approximately 30D-400 C. to produce a cake, grinding and sizing the cake to produce particles of a convenient size, usually from about 4-20 mesh and if necessary subjecting the sized particles to the action of superheated steam at about 265 C. (510 F.) land atmospheric pressure to bring the active catalytic acid toa state of hydration corresponding to maximum efficiency. The above procedure may be modified by extruding and forming the original pasty material and calcining the preformed particles.

The optimum utilization of both the normal and the iso-butenes in the butano-butene mixtures to produce high antiknock iso-octane requires the maximum cross polymerization of isoand normal butenes with the minimum separate polymerization ofnormal or iso-butenes. It has been found that temperatures and pressures must be defined within relatively close limits in order that the iso-octanes produced by the polymerization may be hydrogenated vto high antiknock iso-octanes; The temperatures at which the reaction is preferably initiated fall within the approximate range of 20o-420 F. and the pressures are of the order of 500-'750 pounds per square inch or higher. At higher temperatures and lower pressures the polymerization will produce apparently satisfactory iso-octenes, but when banksA of tubes of vrelatively diameter which are surroundedsby a cooling medium (such as evaporating water) in suitably constructed reactors, and (b) a part of the butanes (possibly containing small percentages of butenes) which are separated from the polymer product after polymerization has taken place, may be returned to the butane-butene charge, thereby reducing the relative amount of reacting hydrocarbons and increasing the relative amount of non-reacting hydrocarbons inthe material passing over the 20 polymerizing catalyst.

The eii'ect oi cooling as described under (a) above generally controls the average temperature at which the catalyst operates, while the eilect' of (b) a partof the butanes (possibly containing small percentages of butenes) which are separated from the polymer product after polymerization has taken place, may be4 returned to the butane-butene charge, thereby reducing the, relative amount'n of reactfns hydrocarbons and in- 3o creasing the relativevamount of non-reacting hydrocarbons in the material passing over the polymerizing catalyst.

The eii'ect of cooling as described under (a) above. generally controls the average vtemperature 35.

at which the catalyst operates, while the eilect of (b) above is to locally avoid the temperature rise of the catalytic surfaces oi' the catalyst particles by lproviding relatively large'quantities of inert material (butanes) as heat absorbing ma- 40 terial at the point where the reaction takes place.

lThe step (b) may be necessary only in cases where the available charging stock is relatively l high in butene content.

A number of reactors may be employed in series so connected that individual reactors may be segregated when the catalyst has become spent,

i ,"in order to replace such spent catalyst while employing other reactors, in which the catalyst has -sumcient activity,A to continue operation. Three such reactors are indicated in the drawings although more may be used. v

From preheater 22 the charge ilows through line 23 containing valve Il and may follow line 2l containing valve 2t and line -21 to enter the upper 55 section 2l of reactor 2l and pass downwardly through the tubes il, containing the pclymerizing catalyst into lower space I'I from which the polymerised olens in admixture'with butanes and butenes leave through line 82, and pass either into 50 ingandhydrogenatingsteplthroughllnewntaining pressure control valve tl which may be automatic.

Reactorlimaybeotthesameconstructionas reactor 2l. containing the same open ting dish'ibu `rspace Ilatthe top.- catalyst tubes Il and lower cllecting space "from whichthereactedhydrocarbons and of butanes and butenes` leavethroughlineandpasseitherthrgh linecontainingvalvelltolinelltoreactcr ceeding fractionating and hydrogenating steps through line Il containing valve Il...

' Line 45 permits the passage of the charge vto reactor 4l which is of the same construction as v reactors 2l and with respect to upper tree space I9, catalyst tubes ,and lower open space li from which polymerlzed products and mixtures o! butanes and butenes pass through line I2 and line Il containing valve 5l to the succeeding fractionating and hydrogenating steps through line ll and valve tl. In order that the reactors may be used in. different order, line I5 containing valve It permits passing the material to line 21 leading into reactor 2l, which will be the case when reactor 4 8 is the nrst of the series and reactor 2l is the second. In this case valve 2t in line 2l will be closed, and valve Il in line I1 will be open. Reactor II is also directly connected to charge line 23 by line il con.

taining valve tl. The connections shown enable the use of -the polymerization reactors in any order in 4a general direction from leit to right as shown in the drawings, and this same general system of operation may be applied to any number of reactors although only three are shown.

'I'he system ot controlling temperature in the reactors may consist of surrounding the tubes with boiling water, the evaporation being maintained by the heat of reaction. The steam generated in the reactors passes through lines Il, 63 and t5, containing valves 62, I3 and 68 respectively through line 01 into disening drum It. In this -drum any water carried by the steam is separated from the steam. The steam passes from the drum Il Vthrough line .I to the preheater 22 or 22', or both as desired, by valves li and I2'. The heat required for preheating the charge is extracted from the steam resulting in its condensation. 'I'he water so formed returns by gravity through line 'Il to drum $8. The water flows from drum Il through line 1| into line 11. Water required for the original filling o i the reactors, or make-up water enters the system through line 12 containing valve 1I and leading into pump 1I. which discharges into line 11. The water may iiow from line 11 into reactors 28, ,and Il through lines 1I, Il, and l2 containing valves 1l, Il, and 83 respectively.

The reactor-cooling and charge-preheating 1 system may operate under two alternative conditions. When the quantity of steam generated actors 2l," and islessthanthesteam con-V densed in preheating the charge in preheater 22, the difference is supplied by adding steam to thesystemfromanoutsidesourcethroghline 8l containing valve l1 and line I8 containing-v down-stream pressure control valve Il. A quantity o f water equivalent vto the steam entering the system through line-- and valve "ls con` tinuously or intermittently withdrawn?through-A line Il containing valve Il. 1

. 'me temperamre at which the reactors n. 36;-

and Il operate'depends on the Vboiling temperatureotthewatermrroimdingthecataly'sthibes, and this boiling temperature is'adiusted'to the a' through line 4| containing valve Q1 to theJuc-Js :desired point at the pressure maintained al 5a cooling system by means of either valve 85 or valve 89.

In order to start the operation of the process the water in reactors 28, 36, and 48 must be heated Yto approximately boiling temperature. Heating this water to this temperature may be accomplished by steam injection by means of steam header 86 and branch lines 92. 94 and 96 containing valves 93, 95 and 91 respectively.

It is to be understood that the method of removing reaction heat herein described constitutes the preferred method, but may be replaced by other suitable methods, such as: the circulation of relatively large quantities of warm liquid cooling medium. The essential features of the cooling system are that it provides on the one hand for effective removal of reaction heat from the catalyst-containing zone, while' on the other hand it prevents any substantial sub-cooling of the reaction zone when the catalyst has become partially spent, or generally in any section of the reactionv zone wherein the reaction proceeds at a reduced rate.

According to the present process the polymer products comprising principally iso-octanes which may be converted into high antiknock iso-octanes when operations have been properly conducted, are first freed of residual butanes and then fractionated to produce mixtures of octenes. For this purpose the products are rst passed to a debutanizer through line 98 containing up-stream pressure control valve 99. Ordinarily the debutam'zer will be operated at a pressure of about 100 pounds per square inch with a top vapor temperature of about 65 C. (150.F.) and a bottom temperature of 196 C. (385 F.) maintained by any type of reboiling coil `shown as |00', which' may permit the passage of steam or process uids as may be convement. 'I'he vapors of butanes pass through line |0| containing up-stream pressure control vvalve |02 and are liquefied during passage through condenser |03 and ilow through line |04 into receiver |05 which has a conventional gas release line |06 containing valve |01. Part of the butanes are withdrawn from the receiver through line |08 and are passed through line |09 containing valve ||0 to pump which discharges through line ||2 containing valve ||3 to the top of the debutanizer in suicient amount to control the character of the. overhead product therefrom. Excess butanes are discharged from the process through line ||4 containing valve ||5. When desired a certain portion of the butane production may be circulated back to the entrance of the polymerization reactors by means of line ||6 containing valve ||1 in order to maintain the concentration of the butenes in the mixture of butanes and butenes passing over the polymerizing catalyst at a xed point to control the temperature rise of the catalytic surfaces by.control1ing the amount of exothermic heat generated relative to the total quantity of material flowing over the catalyst.

The debutanized polymers now pass through line ||8 containing valve/H9 to fractionator |20. If desired a portion of the product at this point may be diverted to storage through line |2| containing valve |22, cooler A|23, and line |24 containing valve |25.

Fractionator |20 is normally operated at a slight superatmospheric pressure of the order of 10 pounds per square inch with a top temperature of 135 C. (275 F.) anda bottom tempera- A ture of 200 C. (390 F.) maintained by reboiling coll |20' as shown. This fractionator preferably functions to remove hydrocarbon materials boiling above octenes or above the nal boiling point required in whatever finished product may be contemplated), the high boiling fractionsleaving the bottom of the column through line |26 .containing valve |21 and thence passing through cooler |28 and line |29 containing valve |30.

The overhead vapors from fractionator |20 comprising principally octenes pass through line |3| containing `valve |32 and through a condenser |33 which has rundown line |34 leading to receiver |35v equipped with the conventional gas release line |36 containing valve |31. The octene fraction accumulating in this receiver passes through a line |36' to pump |31' which returns a sufficient amount of the overhead product through line |38 containing valve |39 to the top of the column to control the character of the overhead product. The octene material produced passes through line |40 to pump |4| and is charged through line |42 containing valve |43 to the nal step of the process involving hydrogenation of the octenes to octanes. Any part of the octene product may also be sent to storage through line |44 containing valve |45.

The general features of the nal hydrogenating unit are oounterflow of hydrogen and octenes in two stages, with recycling of hydrogen in the second stage if required, ,so that the largest proportional amount of hydrogen is admixed with the octenes in their final stage of hydrogenation. Thus the octene fraction is pumped under a pressure of approximately 30 to pounds per square inch throughl a preheater |46 which employs indirect steam contact, while hydrogen from the nal product receiver is added to the octene fraction through line |80. The preheater is preferably operated so that the mixture of hydrogen and octene is heated to a temperature of approximately 2l5 C. (BOZ-419 F.) before entering upper distributing space |48 of primary hydrogenation reactor |41, the mixture passing downwardly through tubes |49 containing hydrogenating catalyst to lower collecting space |50. The partially hydrogenated octenes plus hydrogen (and other fixed gases in case hydrogen-containing gases instead of pure hydrogen are used) pass through line |5| and valve |52 through condenser |53 and line |54 to intermediate receiver |55. Fixed gasesV are vented from the system through line |56 containing upstream pressure control valve |51.l

The partially hydrogenated product then passes to the second stage of hydrogenation throughV line |58, pump |59, and line |60 containing valve |6|. To complete the hydrogenation of the octenes, they are 'mixed with the incoming full supply of hydrogen or hydrogen-containing gas which is admitted through line |62 containing valve |63 and is charged by -compressor |64 through line |65 which joins line |60. The mix- I ture of hydrogen and the partially hydrogenated product then ows through line |66 containing- |13 containing valve |14 through condenser |15 and une m wenn receiver |11 from main product oi the process I containing valve |10.

alinei1 assigne which the is withdrawn through Thegaseswhichareseparatedtromtheiinal product in receiver containing upstream and are added to the octene -frac pressure control preheater I as before described.

oi water Voisteam through4 ing an equal amount In order to increase the hydrogen concen iiow through line i 5 valve Il I tion entering tion in the ilnalstage tojobtain a fully saturated l iinai may be recycled actor I by m` i, compressor line l".

Any type employed though preferred such as,

on a siliceous carrier.

iso-octane product. gases from receiver through preheater l and reof linel III containing valve` ill, and line ill which Joins of hydrogenating catalyst may be the more active varieties are for example. reduced nickel A convenient method of producing anactive catalyst for this process con- .20 sists in precipitating nickel carbonate on kieselguhr, pressing into pills, and then drying and rehydrogen at a temperature ducing directly with oi 400 C. (750 F.) employed such as,

chromium. molybdenum, such cases the pressures time of contact will need tain eiiective saturation.

The hydrogenation reaction in general the same s trol may be utilised as w )throughlines passes valves illand ill `drum i". In this the steam is separated, from steam iiows from the disengaging line ill and continues through line il! and to line in. The heat extracted trom the densation. The wate disengglnl taining valve ill. and to ill containing valve Ill.

riginal nlling oi the reactors.

through line for the o up water, enters the .containing valve III.

-used for discharging system .w The reactor-cooling and mayoperate'undertwo onward required system tions: WhenV the quantity of steam' in reactors M1 and l lis more than when the quantityoi actc'irl |541 and i" is tothesyste'm lesstlianthe4 I l and Il l.,the steamto Less active catalysts may be for example, the oxides 01.25

and tungsten. but in and temperatures and to be increased to obis and 30 ystem of temperature conas described in connecboiling water.' the 3'5 by the heat. of

to reactor It'l conf-50 reactor III through Water or makeline 2li T1115 une my $18013 55 ater from the system charge-preheating alternative condigenerlted thesteamm replacedby chargg through line steam in re,

steam condiilerence 76 the system from "line- III containing valve 2Il. A quanl aient to the steam lll and entering. valve I" l 7s is continuously orv intermittently withdrawn through line 2li containing valve 202.

The temperature at which reactors |41 and l operate depends on the boiling temperature oi the water surrounding the catalyst tubes and this boiling temperature is adjusted to the 'desired point by the pressure maintained on the cooling systemby means oi either valve 2V or valve Ill.

In-order to start the operation oi the process the waterin reactors M1 and i must be heated tov approximately the boiling temperature. Heating the' water may be accomplished by the in- Jection-or steamirom line 2l! through line lll containing valve Ill.

The ionswing'exsmpie is given to indicate the results obtainableby the use oi not with the intent oi un- Ihe catalyst used in tion:

Mol per cent i-Butene n-Butenes Butan'es per square inch. The

.ar r. Rmx,

Gravity i-ocisnesf sas ila-1st 0. (zoo-nso r'.' 4lliklisrboiling polymers 445.5v 171-WC. (M0-8N The composition polymeriaing plant released from the receiver oi the' primary fractionator and produced in an amount oi 66.3% or the charge is shown in the table below:

mol per cent i-Butene 1.7 n -Butene 8.1 Butanes 90.2

The iso-octene traction was then hydrogenated in two stagesbytheuseoiagas'containingavproximateiy'95%' hydrogen gases. methane. In the primary stage of hydrogenation. the temperature was maintained at 190 C. (374 F.)

under a pressure ot approximately poundsper square reactionA therei'ore taking' place substantially in vapor phase. In the secondary stag perature'was again approximately 190 C. (374 1".) but the pressure was app poundspersqnareinchAs by precalcining a mix-l oitheexitgasesiromtheand5%oiotbertreatment a mixture of iso-octanes was produced in an amount equal to 27 per cent by volume of the B-B fraction charged. These iso-octanes had an A. P. I. gravity of 67 and a uniform octane rating of 98 was obtained throughout the operation. The catalyst employed in the hydrogenating reactors consisted of nickel carbonate deposited upon kieselguhr, reduced in an atmosphere of hydrogen.

The nature of the present invention and its practical aspects are evident from the preceding specication and illustrative data although neither section is intended to be unduly limiting.

I claim as my invention:

1. A process for producing iso-octenes which comprises heating a mixture of normally gaseous hydrocarbons containing butenes, contacting the heated materials in a series of reaction zones with an acidic polymerizing catalyst, passing the gaseous hydrocarbons continuously through a series of reaction zones until the catalyst in the first reaction zoneis -appreciably ,reduced in activity, introducing small quantities of a basic nitrogen compound into the second of the series of reaction zones containing the catalyst until the activity of the catalyst in the second zone is reduced, and removing the rst reaction zone from the system, and introducing the gaseous hydrocarbons to the second reaction zone.

2. A process for producing iso-octenes which comprises heating a mixture of normally gaseous hydrocarbons consisting principally of butanes and butenes, contacting the heated materials in a series of reaction zones with an acid polymerizing catalyst comprising a phosphoric acid, passing the gaseous hydrocarbons continuously through a series of reaction zones until the catalyst in the rst reaction zone is appreciably reducedin activity, introducing small quantities of a basic nitrogen compound into the second of the series of reaction zones containing the phosphoric acidcatalyst until the activity of the catalyst in the second zone is reduced, and removing the first reaction zone from the system, and introducing the gaseous hydrocarbons to the second reaction zone.

3. In a4 process for producing iso-octenes wherein a mixture of normally gaseous hydrocarbons consisting principally of butanes and butenes is contacted in a series of reaction zones with polymerizingcatalyst comprising a phosphoricacid, Athe improvement which comprises tion zone with an untreated mixture of basic -introducing gaseous hydrocarbons to the second reaction zone.

CLARENCE G. GERHOLD. 

